CN114478334B - Method for producing dimethyl disulfide by methyl mercaptan vulcanization - Google Patents
Method for producing dimethyl disulfide by methyl mercaptan vulcanization Download PDFInfo
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- CN114478334B CN114478334B CN202210178696.1A CN202210178696A CN114478334B CN 114478334 B CN114478334 B CN 114478334B CN 202210178696 A CN202210178696 A CN 202210178696A CN 114478334 B CN114478334 B CN 114478334B
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- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 title claims abstract description 222
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- 238000004073 vulcanization Methods 0.000 title claims abstract description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 114
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 85
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 85
- YWHLKYXPLRWGSE-UHFFFAOYSA-N Dimethyl trisulfide Chemical compound CSSSC YWHLKYXPLRWGSE-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000007789 gas Substances 0.000 claims abstract description 50
- 229920001021 polysulfide Polymers 0.000 claims abstract description 28
- 239000005077 polysulfide Substances 0.000 claims abstract description 26
- 150000008117 polysulfides Polymers 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 24
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 238000004064 recycling Methods 0.000 claims abstract description 15
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 12
- 238000010521 absorption reaction Methods 0.000 claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 102
- 229910052757 nitrogen Inorganic materials 0.000 claims description 51
- 150000003839 salts Chemical class 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 34
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 29
- 238000004458 analytical method Methods 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000002791 soaking Methods 0.000 claims description 16
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 16
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 238000005507 spraying Methods 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- 239000011593 sulfur Substances 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 5
- 239000003245 coal Substances 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000011982 device technology Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005906 dihydroxylation reaction Methods 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000003879 lubricant additive Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/22—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides
- C07C319/24—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides by reactions involving the formation of sulfur-to-sulfur bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1425—Regeneration of liquid absorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1456—Removing acid components
- B01D53/1468—Removing hydrogen sulfide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/22—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides
Abstract
The invention relates to a method for producing dimethyl disulfide by a methyl mercaptan vulcanization method, which belongs to the technical field of chemical industry, can realize the large-scale utilization of hydrogen sulfide and simultaneously provides a new idea for the comprehensive utilization of hydrogen sulfide in petrochemical industry and coal chemical industry; absorbing effective gases such as hydrogen sulfide in methyl mercaptan synthesis tail gas by adopting low-temperature methanol, resolving the absorption liquid to obtain hydrogen sulfide gas for recycling, and conveying the absorption liquid methanol to a mercaptan reactor for reaction after resolving; methyl mercaptan adopts a high-pressure rectification process, and rectification tail gas returns to methyl mercaptan for synthesis and reuse; the hydrogen sulfide gas obtained by the reaction in the vulcanizing tower is returned to the mercaptan reactor for recycling, and the dimethyl trisulfide and the dimethyl polysulfide generated by the reaction in the vulcanizing tower can be used as the feed of the vulcanizing tower to react with methyl mercaptan to generate dimethyl disulfide, so that the production device has advanced technology, high reaction efficiency, high utilization rate of effective components and small pollution.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a method for producing dimethyl disulfide by a methyl mercaptan vulcanization method.
Background
Dimethyl disulfide is an important chemical product, and can be widely applied to preparing intermediates of pesticide insecticide: in the petroleum industry, the catalyst can be used as an anti-corrosion and anti-coking agent of an ethane cracking furnace, a vulcanizing agent in gasoline hydrogenation catalysis and an inhibitor for hydrocracking in benzene nucleus dehydroxylation reaction; in the rubber industry, can be used as solvents, regenerators, softeners, plasticizers, etc.; in addition, dimethyl disulfide is also useful as a fuel, a lubricant additive, an inhibitor of some organic chemical reactions, and the like. The domestic industrialized production generally adopts a methyl mercaptan method and a dimethyl sulfate method, and the problems of lagging production device technology, low reaction efficiency, difficult recovery of tail gas of mercaptan synthesis, large loss of active components, small scale and large pollution generally exist in the production process of adopting the methyl mercaptan method.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for producing dimethyl disulfide by a methyl mercaptan vulcanization method.
The technical scheme adopted by the invention is as follows: a method for producing dimethyl disulfide by a methyl mercaptan vulcanization method, which comprises the following steps:
step 1, nitrogen is pressurized by a nitrogen fan and then enters an electric heater to be heated, heated nitrogen enters a steam heater to be heated again and then enters a mercaptan reactor to be heated, the nitrogen is discharged from the mercaptan reactor and then returns to the nitrogen fan after being cooled by a nitrogen water cooler, and the nitrogen is circulated to heat the mercaptan reactor to 180-220 ℃ and then stops a nitrogen heating system;
step 2, starting a molten salt pump, enabling molten salt to enter a mercaptan reactor from a molten salt tank to continuously heat the molten salt, returning the molten salt to the molten salt tank after the molten salt comes out of the mercaptan reactor, and circularly heating the mercaptan reactor to 340-380 ℃;
step 3, hydrogen sulfide and methanol enter a mercaptan reactor to react under the action of potassium tungstate serving as a catalyst to generate methyl mercaptan, methyl sulfide and water, wherein the feeding molar ratio of the hydrogen sulfide to the methanol is 1.0-1.3:1.0, the pressure is 0.2-0.4MPa, and the temperature is 340-380 ℃;
step 4, methyl mercaptan, methyl sulfide and water in a mercaptan reactor enter a rectifying tower to carry out rectification, the rectified methyl sulfide is conveyed to the methyl sulfide reactor to react with hydrogen sulfide to generate methyl mercaptan, the rectified methyl mercaptan and the methyl mercaptan in the methyl sulfide reactor are conveyed to a high-pressure tower, the operating pressure of the high-pressure tower is 1.80-1.90MPa, and hydrogen sulfide gas in the methyl mercaptan is separated and then conveyed to a vulcanizing tower;
and 5, filling a soaking solution into a vulcanizing tower filled with catalyst sodium sulfide, keeping the catalyst sodium sulfide immersed in the vulcanizing tower soaking solution, spraying a spraying solution into the vulcanizing tower, continuously introducing methyl mercaptan into the bottom of the vulcanizing tower, reacting under the action of the catalyst sodium sulfide to generate dimethyl disulfide, dimethyl trisulfide, dimethyl polysulfide and hydrogen sulfide gas, returning the hydrogen sulfide gas to a mercaptan reactor for recycling, and carrying out secondary rectification on a mixed solution of the dimethyl disulfide, the dimethyl trisulfide and the dimethyl polysulfide to finally obtain the dimethyl disulfide with the concentration of more than 99.9%.
Further, the method for producing dimethyl disulfide by using the methyl mercaptan vulcanization method further comprises the following steps: the synthesis tail gas in the mercaptan reactor is absorbed by low-temperature methanol through a methanol absorption tower, and then the hydrogen sulfide gas is resolved by a hydrogen sulfide resolving tower and returned to the mercaptan reactor (18) for continuous reaction.
Further, in the method for producing dimethyl disulfide by the methyl mercaptan vulcanization method, before starting a molten salt pump for heating in the step 2, a pipeline electric heater is used for preheating a molten salt pipeline to 180-220 ℃.
Further, in the method for producing dimethyl disulfide by the methyl mercaptan vulcanization method, a steam heater is used for heating nitrogen in step 1 and heating a mixed gas of methanol and hydrogen sulfide in step 3.
Preferably, in the method for producing dimethyl disulfide by using the methyl mercaptan vulcanization method, the soaking solution in the step 5 is a solution containing dimethyl disulfide, dimethyl trisulfide and dimethyl polysulphide.
Preferably, in the method for producing dimethyl disulfide by using the methyl mercaptan vulcanization method, the spray liquid in the step 5 is a solution containing liquid sulfur, dimethyl trisulfide and dimethyl polysulphide.
In the method for producing dimethyl disulfide by using the methyl mercaptan vulcanization method, dimethyl trisulfide and dimethyl polysulfide are recycled as a solvent of liquid sulfur after secondary rectification in the step 5.
Further, in the method for producing dimethyl disulfide by using the methyl mercaptan vulcanization method, the analytic tower comprises an analytic tower water cooler, the analytic tower water cooler is directly connected with the tower body of the analytic tower, the high-pressure tower comprises a high-pressure tower water cooler, and the high-pressure tower water cooler is directly connected with the tower body of the high-pressure tower.
Compared with the prior art, the invention has the beneficial effects that: the method for producing dimethyl disulfide by adopting the methyl mercaptan vulcanization method can realize the large-scale utilization of hydrogen sulfide, and simultaneously provides a new thought for the comprehensive utilization of hydrogen sulfide in petrochemical industry and coal chemical industry; absorbing effective gases such as hydrogen sulfide in methyl mercaptan synthesis tail gas by adopting low-temperature methanol, resolving the absorption liquid to obtain hydrogen sulfide gas for recycling, and conveying the absorption liquid methanol to a mercaptan reactor for reaction after resolving; methyl mercaptan adopts a high-pressure rectification process, and rectification tail gas returns to methyl mercaptan for synthesis and reuse; the hydrogen sulfide gas obtained by the reaction in the vulcanizing tower is returned to the mercaptan reactor for recycling, and the dimethyl trisulfide and the dimethyl polysulfide generated by the reaction in the vulcanizing tower can be used as the feed of the vulcanizing tower to react with methyl mercaptan to generate dimethyl disulfide, so that the recycling of the hydrogen sulfide is improved; the method of nitrogen preheating and molten salt heating avoids the reduction of the activity of the catalyst or the reduction of the service life caused by the too fast temperature rise of the catalyst. The production device has advanced technology, high reaction efficiency, high utilization rate of effective components and little pollution.
Drawings
FIG. 1 is a process flow diagram of the present invention.
In the figure: 1. a nitrogen blower; 2. an electric heater; 3. a steam heater; 4. a mercaptan reactor; 5. a nitrogen water cooler; 6. a molten salt pump; 7. a molten salt tank; 8. a rectifying tower; 9. a dimethyl sulfide reactor; 10. a high pressure column; 11. a vulcanizing tower; 12. a methanol absorption tower; 13. a hydrogen sulfide analysis column; 14. a pipeline electric heater; 15. a water cooler of the analytical tower; 16. a high-pressure tower water cooler.
Detailed Description
The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting the scope of the present invention.
Example 1:
referring to fig. 1, a method for producing dimethyl disulfide by a methyl mercaptan vulcanization method comprises the following steps:
step 1, nitrogen is pressurized by a nitrogen fan 1 and then enters an electric heater 2 to be heated, heated nitrogen enters a steam heater 3 to be heated again and then enters a mercaptan reactor 4 to be heated, the nitrogen is discharged from the mercaptan reactor 4 and then returns to the nitrogen fan 1 after being cooled by a nitrogen water cooler 5, and the nitrogen is circulated to heat the mercaptan reactor 4 to 180 ℃ and then stops a nitrogen heating system;
step 2, preheating a molten salt pipeline to 180 ℃ by using a pipeline electric heater 14, avoiding damage to pipeline expansion caused by too high pipeline heating speed, starting a molten salt pump 6, enabling molten salt to enter a mercaptan reactor 4 from a molten salt tank 7 to continuously heat the molten salt, returning the molten salt to the molten salt tank 7 after the molten salt comes out of the mercaptan reactor 4, circularly heating the mercaptan reactor 4 to 340 ℃, heating by using nitrogen firstly, and then heating by using the molten salt, so that the catalyst activity is reduced or the service life is reduced caused by too fast temperature rising of the catalyst by directly using the molten salt can be avoided;
and step 3, enabling the hydrogen sulfide and the methanol to enter a steam heater 3 to heat the mixed gas of the methanol and the hydrogen sulfide, ensuring that the methanol and the hydrogen sulfide entering the mercaptan reactor are uniformly mixed and have sufficient heat, and ensuring the mercaptan synthesis reaction conditions. The heated hydrogen sulfide and methanol enter a mercaptan reactor 4 to react under the action of potassium tungstate catalyst to generate methyl mercaptan, methyl sulfide and water, wherein the feeding mole ratio of the hydrogen sulfide to the methanol is 1:1, the pressure is 0.2, and the temperature is 340 ℃. The synthesis tail gas in the mercaptan reactor 4 is absorbed into hydrogen sulfide by using low-temperature methanol through a methanol absorption tower 12, and then the hydrogen sulfide gas analyzed by a hydrogen sulfide analysis tower 13 is returned to the mercaptan reactor 4 for continuous reaction. The hydrogen sulfide analysis tower 13 comprises an analysis tower water cooler 15, the analysis tower water cooler 9 is directly connected with the tower body of the hydrogen sulfide analysis tower 13, the high-pressure tower 10 comprises a high-pressure tower water cooler 16, and the high-pressure tower water cooler 16 is directly connected with the tower body of the high-pressure tower 10, so that leakage caused by material pipeline transmission is avoided, and the safety of equipment is improved;
step 4, methyl mercaptan, methyl sulfide and water in the mercaptan reactor 4 enter a rectifying tower 8 for rectification, the rectified methyl sulfide is conveyed to a methyl sulfide reactor 9 to react with hydrogen sulfide to generate methyl mercaptan, the rectified methyl mercaptan and the methyl mercaptan in the methyl sulfide reactor 9 are conveyed to a high-pressure tower 10, the operating pressure of the high-pressure tower 10 is 1.80MPa, hydrogen sulfide gas in the methyl mercaptan is separated and then conveyed to a vulcanizing tower 11, and the hydrogen sulfide gas is separated and reused after the high-pressure tower 10 is rectified at high pressure, so that the purity of the refined methyl mercaptan is improved, and the vulcanizing tower reaction is facilitated;
and 5, filling a soaking solution containing dimethyl disulfide, dimethyl trisulfide and dimethyl polysulfide solution into a vulcanizing tower 11 filled with sodium sulfide as a catalyst, keeping the sodium sulfide as a catalyst immersed in the soaking solution of the vulcanizing tower 11, spraying a spraying solution containing liquid sulfur, dimethyl trisulfide and dimethyl polysulfide solution into the soaking solution, continuously introducing methyl mercaptan into the bottom of the vulcanizing tower 11, reacting under the action of the sodium sulfide as a catalyst to generate dimethyl disulfide, dimethyl trisulfide, dimethyl polysulfide and hydrogen sulfide gas, returning the hydrogen sulfide gas to a mercaptan reactor 4 for recycling, and finally obtaining 99.91% of dimethyl disulfide by secondary rectification of the mixed solution of dimethyl disulfide, dimethyl trisulfide and dimethyl polysulfide, and recycling the dimethyl trisulfide as a solvent of the liquid sulfur after the secondary rectification.
Example 2:
referring to fig. 1, a method for producing dimethyl disulfide by a methyl mercaptan vulcanization method comprises the following steps:
step 1, nitrogen is pressurized by a nitrogen fan 1 and then enters an electric heater 2 to be heated, the heated nitrogen enters a steam heater 3 to be heated again and then enters a mercaptan reactor 4 to be heated, the nitrogen is discharged from the mercaptan reactor 4 and then returns to the nitrogen fan 1 after being cooled by a nitrogen water cooler 5, the nitrogen circularly heats the mercaptan reactor 4 to 200 ℃, and a nitrogen heating system is stopped;
step 2, preheating a molten salt pipeline to 200 ℃ by using a pipeline electric heater 14, starting a molten salt pump 6, enabling molten salt to enter a mercaptan reactor 4 from a molten salt tank 7 to continuously heat the molten salt, returning the molten salt to the molten salt tank 7 after the molten salt comes out of the mercaptan reactor 4, and circularly heating the mercaptan reactor 4 to 360 ℃;
and 3, enabling hydrogen sulfide and methanol to enter a steam heater 3 to heat a mixed gas of the methanol and the hydrogen sulfide, enabling the heated hydrogen sulfide and the heated methanol to enter a mercaptan reactor 4 to react under the action of a catalyst potassium tungstate to generate methyl mercaptan, methyl sulfide and water, wherein the feeding mole ratio of the hydrogen sulfide to the methanol is 1.1:1.0, the pressure is 0.3MPa, and the temperature is 360 ℃. The synthesis tail gas in the mercaptan reactor 4 is absorbed into hydrogen sulfide by using low-temperature methanol through a methanol absorption tower 12, and then the hydrogen sulfide gas analyzed by a hydrogen sulfide analysis tower 13 is returned to the mercaptan reactor 4 for continuous reaction. The hydrogen sulfide analysis tower 13 comprises an analysis tower water cooler 15, the analysis tower water cooler 9 is directly connected with the tower body of the hydrogen sulfide analysis tower 13, the high-pressure tower 10 comprises a high-pressure tower water cooler 16, and the high-pressure tower water cooler 16 is directly connected with the tower body of the high-pressure tower 10;
step 4, methyl mercaptan, methyl sulfide and water in the mercaptan reactor 4 enter a rectifying tower 8 for rectification, the rectified methyl sulfide is conveyed to a methyl sulfide reactor 9 to react with hydrogen sulfide to generate methyl mercaptan, the rectified methyl mercaptan and the methyl mercaptan in the methyl sulfide reactor 9 are conveyed to a high-pressure tower 10, the operating pressure of the high-pressure tower 10 is 1.88MPa, hydrogen sulfide gas in the methyl mercaptan is separated and then conveyed to a vulcanizing tower 11, and the hydrogen sulfide gas is separated and reused after the high-pressure tower 10 is rectified at high pressure, so that the purity of the refined methyl mercaptan is improved, and the vulcanizing tower reaction is facilitated;
and 5, filling a soaking solution containing dimethyl disulfide, dimethyl trisulfide and dimethyl polysulfide solution into a vulcanizing tower 11 filled with sodium sulfide as a catalyst, keeping the sodium sulfide as a catalyst immersed in the soaking solution of the vulcanizing tower 11, spraying a spraying solution containing liquid sulfur, dimethyl trisulfide and dimethyl polysulfide solution into the soaking solution, continuously introducing methyl mercaptan into the bottom of the vulcanizing tower 11, reacting under the action of the sodium sulfide as a catalyst to generate dimethyl disulfide, dimethyl trisulfide, dimethyl polysulfide and hydrogen sulfide gas, returning the hydrogen sulfide gas to a mercaptan reactor 4 for recycling, and finally obtaining 99.96% of dimethyl disulfide by secondary rectification of the mixed solution of dimethyl disulfide, dimethyl trisulfide and dimethyl polysulfide, and recycling the dimethyl trisulfide as a solvent of the liquid sulfur after the secondary rectification.
Example 3:
referring to fig. 1, a method for producing dimethyl disulfide by a methyl mercaptan vulcanization method comprises the following steps:
step 1, nitrogen is pressurized by a nitrogen fan 1 and then enters an electric heater 2 to be heated, heated nitrogen enters a steam heater 3 to be heated again and then enters a mercaptan reactor 4 to be heated, the nitrogen is discharged from the mercaptan reactor 4 and then returns to the nitrogen fan 1 after being cooled by a nitrogen water cooler 5, and the nitrogen is circulated to heat the mercaptan reactor 4 to 220 ℃, and then a nitrogen heating system is stopped;
step 2, preheating a molten salt pipeline to 220 ℃ by using a pipeline electric heater 14, starting a molten salt pump 6, enabling molten salt to enter a mercaptan reactor 4 from a molten salt tank 7 to continuously heat the molten salt, returning the molten salt to the molten salt tank 7 after the molten salt comes out of the mercaptan reactor 4, and circularly heating the mercaptan reactor 4 to 380 ℃;
step 3, hydrogen sulfide and methanol enter a steam heater 3 to heat mixed gas of the methanol and the hydrogen sulfide, the heated hydrogen sulfide and the heated methanol enter a mercaptan reactor 4 to react under the action of potassium tungstate serving as a catalyst to generate methyl mercaptan, methyl sulfide and water, the feeding mole ratio of the hydrogen sulfide to the methanol is 1.0-1.3:1.0, the pressure is 0.2-0.4MPa, and the temperature is 340-380 ℃. The synthesis tail gas in the mercaptan reactor 4 is absorbed into hydrogen sulfide by using low-temperature methanol through a methanol absorption tower 12, and then the hydrogen sulfide gas analyzed by a hydrogen sulfide analysis tower 13 is returned to the mercaptan reactor 4 for continuous reaction. The hydrogen sulfide analysis tower 13 comprises an analysis tower water cooler 15, the analysis tower water cooler 9 is directly connected with the tower body of the hydrogen sulfide analysis tower 13, the high-pressure tower 10 comprises a high-pressure tower water cooler 16, and the high-pressure tower water cooler 16 is directly connected with the tower body of the high-pressure tower 10.
Step 4, methyl mercaptan, methyl sulfide and water in the mercaptan reactor 4 enter a rectifying tower 8 for rectification, the rectified methyl sulfide is conveyed to a methyl sulfide reactor 9 to react with hydrogen sulfide to generate methyl mercaptan, the rectified methyl mercaptan and the methyl mercaptan in the methyl sulfide reactor 9 are conveyed to a high-pressure tower 10, the operating pressure of the high-pressure tower 10 is 1.90MPa, hydrogen sulfide gas in the methyl mercaptan is separated and then conveyed to a vulcanizing tower 11, and the hydrogen sulfide gas is separated and reused after the high-pressure tower 10 is rectified at high pressure, so that the purity of the refined methyl mercaptan is improved, and the vulcanizing tower reaction is facilitated;
and 5, filling a soaking solution containing dimethyl disulfide, dimethyl trisulfide and dimethyl polysulfide solution into a vulcanizing tower 11 filled with sodium sulfide as a catalyst, keeping the sodium sulfide as a catalyst immersed in the soaking solution of the vulcanizing tower 11, spraying a spraying solution containing liquid sulfur, dimethyl trisulfide and dimethyl polysulfide solution into the soaking solution, continuously introducing methyl mercaptan into the bottom of the vulcanizing tower 11, reacting under the action of the sodium sulfide as a catalyst to generate dimethyl disulfide, dimethyl trisulfide, dimethyl polysulfide and hydrogen sulfide gas, returning the hydrogen sulfide gas to a mercaptan reactor 4 for recycling, and finally obtaining 99.92% of dimethyl disulfide by secondary rectification of the mixed solution of dimethyl disulfide, dimethyl trisulfide and dimethyl polysulfide, and recycling the dimethyl trisulfide as a solvent of the liquid sulfur after the secondary rectification.
The working principle and the using flow of the invention are as follows:
the nitrogen is pressurized by a nitrogen fan 1 and then enters an electric heater 2 to be heated, the heated nitrogen enters a steam heater 3 to be heated again and then enters a mercaptan reactor 4 to be heated, and the gas discharged from the mercaptan reactor 4 is cooled by a nitrogen water cooler 5 and then returns to the nitrogen fan 1 to be circularly heated; the pipeline electric heater 14 is operated to heat the molten salt pipeline, and the heating system is stopped after the temperature of the mercaptan reactor 4 and the molten salt pipeline is raised to 180-220 ℃. The molten salt pump 6 is operated to heat the mercaptan reactor 4 to 340-380 ℃, hydrogen sulfide and methanol start to feed, the materials enter the mercaptan reactor 4 to react under the action of catalyst potassium tungstate to generate methyl mercaptan, methyl sulfide and water, the molar ratio of the hydrogen sulfide to the methanol is 1.0-1.3:1.0, the pressure is 0.2-0.4MPa, the temperature is 340-380 ℃, sulfide by-produced in the mercaptan reactor 4 is conveyed to the methyl sulfide reactor 9 to react with the hydrogen sulfide to generate methyl mercaptan after rectification, the methyl mercaptan removes dissolved hydrogen sulfide gas through the high-pressure tower 10, the operating pressure of the high-pressure tower 10 is 1.80-1.90MPa, and the hydrogen sulfide gas returns to the mercaptan reactor 4 to continue to react. The synthesis tail gas is absorbed by low-temperature methanol through a methanol absorption tower 12, and then the hydrogen sulfide gas is analyzed by a hydrogen sulfide analysis tower 13 and returned to the mercaptan reactor 4 for continuous reaction. The method comprises the steps of filling a mixed solution containing dimethyl disulfide, dimethyl trisulfide and dimethyl polysulfide into a vulcanizing tower 11 filled with sodium sulfide as a catalyst, keeping the catalyst immersed in the solution in the tower, spraying liquid sulfur, dimethyl trisulfide and dimethyl polysulfide mixed solution, continuously introducing methyl mercaptan into the bottom of the vulcanizing tower 11, reacting under the action of the catalyst to generate dimethyl disulfide, dimethyl trisulfide, dimethyl polysulfide and hydrogen sulfide gas, returning the hydrogen sulfide gas to a mercaptan reactor 4 for recycling, recycling the dimethyl trisulfide and the dimethyl polysulfide as a solvent of the liquid sulfur through secondary rectification to obtain the dimethyl disulfide with the purity reaching more than 99.9 percent.
It will be apparent that the embodiments described above are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Claims (6)
1. A method for producing dimethyl disulfide by a methyl mercaptan vulcanization method, which is characterized by comprising the following steps:
step 1, nitrogen is pressurized by a nitrogen fan (1) and then enters an electric heater (2) to be heated, heated nitrogen enters a steam heater (3) to be heated again and then enters a mercaptan reactor (4) to be heated, the nitrogen is discharged from the mercaptan reactor (4) and then is cooled by a nitrogen water cooler (5) and then returns to the nitrogen fan (1), and the nitrogen is circulated to heat the mercaptan reactor (4) to 180-220 ℃, and then the nitrogen heating system is stopped;
step 2, starting a molten salt pump (6), enabling molten salt to enter a mercaptan reactor (4) from a molten salt tank (7) to continuously heat the molten salt, enabling the molten salt to return to the molten salt tank (7) after coming out of the mercaptan reactor (4), and circularly heating the mercaptan reactor (4) to 340-380 ℃;
step 3, hydrogen sulfide and methanol enter a mercaptan reactor (4) to react under the action of potassium tungstate serving as a catalyst to generate methyl mercaptan, methyl sulfide and water, wherein the feeding mole ratio of the hydrogen sulfide to the methanol is 1.0-1.3:1.0, the pressure is 0.2-0.4MPa, and the temperature is 340-380 ℃;
step 4, methyl mercaptan, methyl sulfide and water in the mercaptan reactor (4) enter a rectifying tower (8) for rectification, the rectified methyl sulfide is conveyed to a methyl sulfide reactor (9) to react with hydrogen sulfide to generate methyl mercaptan, the rectified methyl mercaptan and the methyl mercaptan in the methyl sulfide reactor (9) are conveyed to a high-pressure tower (10), the operating pressure of the high-pressure tower (10) is 1.80-1.90MPa, and hydrogen sulfide gas in the methyl mercaptan is separated and then conveyed to a vulcanizing tower (11);
and 5, filling a soaking solution into a vulcanizing tower (11) filled with catalyst sodium sulfide, keeping the catalyst sodium sulfide immersed in the soaking solution of the vulcanizing tower (11), spraying a spraying solution into the soaking solution, continuously introducing methyl mercaptan into the bottom of the vulcanizing tower (11), reacting under the action of the catalyst sodium sulfide to generate dimethyl disulfide, dimethyl trisulfide, dimethyl polysulfide and hydrogen sulfide gas, returning the hydrogen sulfide gas to a mercaptan reactor (4) for recycling, and carrying out secondary rectification on a mixed solution of the dimethyl disulfide, the dimethyl trisulfide and the dimethyl polysulfide to finally obtain the dimethyl disulfide with the concentration of more than 99.9%, wherein the soaking solution is a solution containing dimethyl disulfide, dimethyl trisulfide and dimethyl polysulfide, and the spraying solution is a solution containing liquid sulfur, dimethyl trisulfide and dimethyl polysulfide.
2. The method for producing dimethyl disulfide by a methyl mercaptan vulcanization process according to claim 1, characterized by further comprising the steps of: the synthesis tail gas in the mercaptan reactor (4) absorbs hydrogen sulfide by utilizing low-temperature methanol through a methanol absorption tower (12), and then the hydrogen sulfide gas is analyzed by utilizing a hydrogen sulfide analysis tower (13) and returned to the mercaptan reactor (4) for continuous reaction.
3. The method for producing dimethyl disulfide by methyl mercaptan vulcanization according to claim 1, characterized in that: and (2) preheating a molten salt pipeline to 180-220 ℃ by using a pipeline electric heater (14) before starting a molten salt pump (6) for heating in the step (2).
4. The method for producing dimethyl disulfide by methyl mercaptan vulcanization according to claim 1, characterized in that: the steam heater (3) is used to heat nitrogen in step 1 and to heat a mixture of methanol and hydrogen sulfide in step 3.
5. The method for producing dimethyl disulfide by methyl mercaptan vulcanization according to claim 1, characterized in that: in the step 5, dimethyl trisulfide and dimethyl polysulfide are circularly used as a solvent of liquid sulfur after secondary rectification.
6. The method for producing dimethyl disulfide by methyl mercaptan vulcanization according to claim 2, characterized in that: the hydrogen sulfide analysis tower (13) comprises an analysis tower water cooler (15), the analysis tower water cooler (15) is directly connected with the tower body of the hydrogen sulfide analysis tower (13), the high-pressure tower (10) comprises a high-pressure tower water cooler (16), and the high-pressure tower water cooler (16) is directly connected with the tower body of the high-pressure tower (10).
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